Compound and organic electronic device comprising the same

ABSTRACT

A novel compound is disclosed, which is represented by the following Formula (I): 
     
       
         
         
             
             
         
       
     
     wherein Ar 1 , Ar 2 , Ar 3 , Ar 4 , L, Q, G, n1, n2, m1, m2 and q represent the same as defined in the specification. In addition, an organic electronic device is also disclosed, and an organic layer therein comprises the novel compound of the present invention.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of filing date of U.S. ProvisionalApplication Ser. No. 62/287,724, entitled “Novel Compound and OrganicElectronic Device Using the Same” filed Jan. 27, 2016 under 35 USC §119(e)(1).

BACKGROUND

1. Field

The present invention relates to a novel compound and an organicelectronic device using the same.

2. Description of Related Art

It is well known that organic light emitting device (OLED device) wasinitially invented and proposed by Eastman Kodak Company through avacuum evaporation method. Tang and VanSlyke of Kodak Company depositedan electron transport material such as Alq₃ on a transparent indium tinoxide (abbreviated as ITO) glass formed with an organic layer ofaromatic diamine thereon, and subsequently completed the fabrication ofan organic electroluminescent (EL) device after a metal electrode isvapor-deposited onto the Alq₃ layer. The organic EL device currentlybecomes a new generation lighting device or display because of highbrightness, fast response speed, light weight, compactness, true color,no difference in viewing angles, without using any LCD backlight plates,and low power consumption.

Recently, some interlayers such as electron transport layer and holetransport layer are added between the cathode and the anode forincreasing the current efficiency and power efficiency of the OLEDs. Forexample, an organic light emitting diode (OLED) 1′ shown as FIG. 1 isdesigned to consist of: a cathode 11′, an electron injection layer 13′,a light emitting layer 14′, a hole transport layer 16′, and an anode18′.

Recently, for effectively increasing the lighting performance of OLEDs,OLED manufactures and researchers have made great efforts to developdifferent compounds used as the materials for the OLEDs. However, inspite of various compounds have been developed, the currentphosphorescence OLEDs still cannot perform outstanding luminousefficiency and device lifetime. Accordingly, in view of the conventionalor commercial materials for OLEDs still including drawbacks, theinventor of the present application has made great efforts to makeinventive research thereon and eventually provided novel compounds forOLED.

SUMMARY

The object of the present disclosure is to provide a novel compound andan organic electronic device comprising the same.

According to one or more embodiments, a compound is represented byFormula (I) below:

wherein,

Ar₁, Ar₂, Ar₃, and Ar₄ are each independently hydrogen, deuterium, asubstituted or unsubstituted C₁-C₂₀ alkyl group, a substituted orunsubstituted C₆-C₄₀ aryl group, a substituted or unsubstituted C₁-C₄₀heterocyclic group, or a substituted or unsubstituted amine group; orAr₁ and Ar₂ together with the nitrogen atom to which they are bonded isa substituted or unsubstituted C₁-C₄₀ heterocyclic group; or Ar₃ and Ar₄together with the nitrogen atom to which they are bonded is asubstituted or unsubstituted C₁-C₄₀ heterocyclic group;

L and Q are each independently a substituted or unsubstituted C₆-C₄₀arylene group;

G is deuterium, a substituted or unsubstituted C₁-C₂₀ alkyl group, asubstituted or unsubstituted C₆-C₄₀ aryl group, a substituted orunsubstituted C₁-C₄₀ heterocyclic group, or —NR₁R₂;

R₁ and R₂ are each independently hydrogen, deuterium, a substituted orunsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstituted C₆-C₄₀aryl group, or a substituted or unsubstituted C₁-C₄₀ heterocyclic group;

n1 and n2 are each independently 0 or 1;

m1 and m2 are each independently 0, 1 or 2, and with the proviso that m1and m2 are not 0 at the same time; and

q is 0, 1, or 2.

According to one or more embodiments, an organic electronic devicecomprises: a first electrode; a second electrode; and an organic layerdisposed between the first electrode and the second electrode, whereinthe organic layer comprises the compound of the aforesaid Formula (I).

The present disclosure provides a novel compound. When the compound ofthe present disclosure is used in an organic electronic device, theefficiency of the organic electronic device can be improved. Especially,when the novel compound of the present disclosure is used as onematerial of an organic light emitting device, the luminous efficiency ofthe organic light emitting device can further be improved.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view showing an OLED device of the prior art;

FIG. 2 is a perspective view showing an OLED device of the presentinvention; and

FIG. 3 is a perspective view showing an organic solar cell device of thepresent invention.

FIG. 4 is 1H NMR data of Compound (1) (SGM134) of the presentdisclosure.

FIG. 5 is 1H NMR data of Compound (2) (SGM137) of the presentdisclosure.

FIG. 6 is 1H NMR data of Compound (4) (SGM423) of the presentdisclosure.

FIG. 7 is 1H NMR data of Compound (7) (SGM135) of the presentdisclosure.

FIG. 8 is 1H NMR data of Compound (8) (SGM138) of the presentdisclosure.

FIG. 9 is 1H NMR data of Compound (10) (SGM422) of the presentdisclosure.

FIG. 10 is 1H NMR data of Compound (11) (SGM565) of the presentdisclosure.

FIG. 11 is 1H NMR data of Compound (12) (SGM578) of the presentdisclosure.

FIG. 12 is 1H NMR data of Compound (31) (SGM564) of the presentdisclosure.

FIG. 13 is 1H NMR data of Compound (13) (SGM136) of the presentdisclosure.

FIG. 14 is 1H NMR data of Compound (14) (SGM139) of the presentdisclosure.

FIG. 15 is 1H NMR data of Compound (15) (SGM171) of the presentdisclosure.

FIG. 16 is 1H NMR data of Compound (20) (SGM567) of the presentdisclosure.

FIG. 17 is 1H NMR data of Compound (21) (SGM568) of the presentdisclosure.

FIG. 18 is 1H NMR data of Compound (30) (SGM557) of the presentdisclosure.

FIG. 19 is 1H NMR data of Compound (32) (SGM584) of the presentdisclosure.

FIG. 20 is 1H NMR data of Compound (33) (SGM594) of the presentdisclosure.

DETAILED DESCRIPTION

Hereinafter, the present disclosure is described in detail. The presentdisclosure has been described in an illustrative manner, and it is to beunderstood that the terminology used is intended to be in the nature ofdescription rather than of limitation. Many modifications and variationsof the present disclosure are possible in light of the teachings.Therefore, it is to be understood that within the scope of the appendedclaims, the invention may be practiced otherwise than as specificallydescribed.

Compound

A compound according to one exemplary embodiment may be represented bythe following Formula (I).

In formula (I), Ar₁, Ar₂, Ar₃, and Ar₄ may be each independentlyhydrogen, deuterium, a substituted or unsubstituted C₁-C₂₀ alkyl group,a substituted or unsubstituted C₆-C₄₀ aryl group, a substituted orunsubstituted C₁-C₄₀ heterocyclic group, or a substituted orunsubstituted amine group; or Ar₁ and Ar₂ together with the nitrogenatom to which they are bonded may be a substituted or unsubstitutedC₁-C₄₀ heterocyclic group; or Ar₃ and Ar₄ together with the nitrogenatom to which they are bonded may be a substituted or unsubstitutedC₁-C₄₀ heterocyclic group;

L and Q may be each independently a substituted or unsubstituted C₆-C₄₀arylene group;

G may be deuterium, a substituted or unsubstituted C₁-C₂₀ alkyl group, asubstituted or unsubstituted C₆-C₄₀ aryl group, a substituted orunsubstituted C₁-C₄₀ heterocyclic group, or —NR₁R₂;

R₁ and R₂ may be each independently hydrogen, deuterium, a substitutedor unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstitutedC₆-C₄₀ aryl group, or a substituted or unsubstituted C₁-C₄₀ heterocyclicgroup;

n1 and n2 may be each independently 0 or 1;

m1 and m2 may be each independently 0, 1 or 2, and with the proviso thatm1 and m2 are not 0 at the same time; and

q may be 0, 1, or 2.

According to one embodiment, Ar₁, Ar₂, Ar₃, and Ar₄ can be eachindependently a substituted or unsubstituted C₆-C₄₀ aryl group, or asubstituted or unsubstituted C₁-C₄₀ heterocyclic group; or Ar₁ and Ar₂together with the nitrogen atom to which they are bonded can be asubstituted or unsubstituted C₁-C₄₀ heterocyclic group; or Ar₃ and Ar₄together with the nitrogen atom to which they are bonded can be asubstituted or unsubstituted C₁-C₄₀ heterocyclic group. Preferably, Ar₁,Ar₂, Ar₃, and Ar₄ are each independently a substituted or unsubstitutedC₆-C₄₀ aryl group, or a substituted or unsubstituted C₁-C₄₀ heteroarylgroup; or Ar₁ and Ar₂ together with the nitrogen atom to which they arebonded is a substituted or unsubstituted C₁-C₄₀ heteroaryl group; or Ar₃and Ar₄ together with the nitrogen atom to which they are bonded is asubstituted or unsubstituted C₁-C₄₀ heteroaryl group.

According to one embodiment, Ar₁, Ar₂, Ar₃, and Ar₄ may be eachindependently substituted or unsubstituted phenyl, substituted orunsubstituted biphenyl, substituted or unsubstituted terphenyl,substituted or unsubstituted fluorenyl, substituted or unsubstitutedtribenzyloxepinyl, substituted or unsubstituted dibenzofuranyl,substituted or unsubstituted dibenzothiofuranyl, substituted orunsubstituted naphthyl, or substituted or unsubstitutedtribenzyl-azepinyl group. Preferably, Ar₁, Ar₂, Ar₃, and Ar₄ are eachindependently unsubstituted phenyl, phenyl substituted with alkyl,unsubstituted biphenyl, unsubstituted terphenyl, unsubstitutedfluorenyl, fluorenyl substituted with alkyl, unsubstitutedtribenzyloxepinyl, unsubstituted dibenzofuranyl, or unsubstitutednaphthyl.

According to one embodiment, m1 may be 1; and m2 may be 0 or 1.According to another embodiment, m1 may be 1 and m2 may be 0. Accordingto further another embodiment, m1 may be 1 and m2 may be 1.

According to one embodiment, m1 may be 1; m2 may be 0; and Ar₁ and Ar₂together with the nitrogen atom to which they are bonded may be asubstituted or unsubstituted C₁-C₄₀ heteroaryl group. Preferably, Ar₁and Ar₂ together with the nitrogen atom to which they are bonded isunsubstituted tribenzyl-azepinyl group.

According to one embodiment, when m1 and m2 are not 0 at the same time,-L_(n1)-NAr₁Ar₂ and -Q_(n2)-NAr₃Ar₄ can be the same.

According to one embodiment, m1 and m2 are 1, and -L_(n1)-NAr₁Ar₂ and-Q_(n2)-NAr₃Ar₄ can be the same.

According to one embodiment, L and Q may be each independentlysubstituted or unsubstituted phenylene, biphenylene, or naphthylene.Preferably, L and Q are each independently unsubstituted phenylene.

According to one embodiment, q may 0 or 1.

When q is 1, G may be a substituted or unsubstituted C₆-C₄₀ aryl group,a substituted or unsubstituted C₁-C₄₀ heterocyclic group, or —NR₁R₂, inwhich R₁ and R₂ are each independently a substituted or unsubstitutedC₆-C₄₀ aryl group. Preferably, G is a substituted or unsubstitutedC₁-C₄₀ heteroaryl group containing a nitrogen atom, or —NR₁R₂, in whichR₁ and R₂ are the same and are a substituted or unsubstituted phenyl,biphenyl or naphthylene. More preferably, G is unsubstituted pyridyl, or—NR₁R₂, in which R₁ and R₂ are unsubstituted phenyl.

According to one embodiment, G, -L_(n1)-NAr₁Ar₂ and -Q_(n2)-NAr₃Ar₄ canbe the same. For example, when m1 is 1 and m2 is 0, G and-L_(n1)-NAr₁Ar₂ can be the same.

According to another embodiment G, -L_(n1)-NAr₁Ar₂ and -Q_(n2)-NAr₃Ar₄can be different. For example, when m1 is 1 and m2 is 0, G and-L_(n1)-NAr₁Ar₂ can be different.

According to one embodiment, the compound of Formula (I) can berepresented by any one of Formulas (I-1) to (I-18) below.

Ar₁, Ar₂, Ar₃, Ar₄, L, Q, G, n1, and n2 in Formulas (I-1) to (I-18)represent the same as those described above.

According to one embodiment, -L_(n1)-NAr₁Ar₂ and -Q_(n2)-NAr₃Ar₄ can beeach independently selected from the group consisting of:

wherein * represents bonding positions, Ra and Rb are each independentlyC₁₋₂₀ alkyl, and x and y are each independently 1 or 2. Herein, Ra andRb can be the same. X and y can be the same. Examples of Ra and Rb canbe methyl, ethyl or propyl. In addition, n1 or n2 can be 0.

According to one embodiment, n1 is 0 and n2 is 1. According to anotherembodiment, n1 is 1 and n2 is 1. In these two embodiments,L_(n1)-NAr₁Ar₂ and -Q_(n2)-NAr₃Ar₄ can be each independently selectedfrom the group consisting of:

wherein * represents bonding positions. The definitions of Ra, Rb, x andy are the same as those illustrated above. In these two embodiments, Land Q can be each independently a substituted or unsubstituted C₆-C₄₀arylene group such as phenylene.

Hereinafter, substitutes of Formula (I) is described in detail.Substitutes that are not defined in the present disclosure are definedas known in the art.

In the present disclosure, the unsubstituted alkyl group can be linearor branched. Examples of the alkyl group include C₁-C₂₀ alkyl, C₁₋₁₀alkyl, or C₁₋₆ alkyl. Specific examples of the unsubstituted alkyl groupinclude, but are not limited to, methyl, ethyl, n-propyl, iso-propyl,n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, neo-pentyl, or hexyl.Herein, at least one hydrogen atom of the unsubstituted alkyl group maybe substituted with a halogen group, an alkyl group, an alkenyl group,an alkoxy group, a cycloalkyl group, an aryl group, an arylalkyl group,an arylalkenyl group, a heterocyclic group, a nitrile group, or anacetylene group.

In the present disclosure, the unsubstituted aryl group refers toaromatic hydrocarbon group. Examples of the aryl group can be C₆-C₄₀aryl, or C₆-C₂₀ aryl. In addition, examples of the aryl group can amonocyclic, bicyclic, tricyclic, or polycyclic aromatic hydrocarbongroup; wherein two or more rings may be fused to each other or linked toeach other via a single bond. Specific examples of the unsubstitutedaryl group include, but are not limited to phenyl, biphenylyl,terphenyl, quarterphenyl, naphthyl, anthryl, benzanthryl, phenanthryl,naphthacenyl, pyrenyl, chrysenyl, benzo[c]phenanthryl,benzo[g]chrysenyl, triphenylenyl, fluorenyl, spirobifluorenyl,benzofluorenyl, or dibenzofluorenyl. Herein, at least one hydrogen atomof the unsubstituted aryl group may be substituted with the samesubstituents described above related to the alkyl group. In addition,the definition of the arylene group is similar to those stated above,and the detail description of the arylene group is not repeated herein.

In the present disclosure, the unsubstituted heterocyclic group refersto non-aromatic or aromatic hydrocarbon group. Examples of theheterocyclic group can be a C₁-C₄₀ heterocyclic group, C₂-C₂₀heterocyclic group or a C₄-C₂₀ heterocyclic group. In addition, examplesof the heterocyclic group can be a monocyclic, bicyclic, tricyclic, orpolycyclic heteroaryl or heterocycloalkyl having at least one heteroatomwhich is selected from the group consisting of O, S and N; wherein twoor more rings may be fused to each other or linked to each other via asingle bond. Specific examples of the unsubstituted heterocyclic groupinclude, but are not limited to, pyroryl, pyrazinyl, pyridinyl,piperidinyl, indolyl, isoindolyl, imidazolyl, benzoimidazolyl, furyl,ozazolyl, thiazolyl, triazolyl, thiadiazolyl, benzothiazolyl,tetrazolyl, oxadiazolyl, triazinyl, carbazolyl, benzofuranyl,isobenzofuranyl, dibenzofuranyl, dibenzothiofuranyl, dibenzothiophenyl,quinolyl, isoquinolyl, quinoxalinyl, phenantridinyl, acridinyl,phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazolyl,oxadiazoyl, furazanyl, thienyl, benzothiophenyl, tribenzyloxepinyl,thiophenyl, or benzooxazolyl. Herein, at least one hydrogen atom of theunsubstituted heterocyclic group may be substituted with the samesubstituents described above related to the alkyl group.

In one embodiment, two or more aryl or hetero rings may be directlylinked to each other to form a spiro structure. For example, fluorenyland tribenzo-cycloheptatrienyl may be linked to each other to form aSpiro structure.

In the present disclosure, halogen includes F, Cl, Br and I; andpreferably is F or Br.

In the present disclosure, the unsubstituted alkoxy group refers to amoiety that the alkyl defined above coupled with an oxygen atom.Examples of the alkoxy group can include linear or branched C₁₋₁₀alkoxy, or linear or branched C₁₋₆ alkoxy. Specific examples of alkoxyinclude, but are not limited to, methoxy, ethoxy, n-propoxy,iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy,neo-pentyloxy or hexyloxy. Herein, at least one hydrogen atom of theunsubstituted alkoxy group may be substituted with the same substituentsdescribed above related to the alkyl group.

In the present disclosure, the unsubstituted cycloalkyl group refers toa monovalent saturated hydrocarbon ring system having 3 to 20 carbonatoms, or 3 to 12 carbon atoms. Specific examples of the unsubstitutedcycloalkyl group include, but are not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.Herein, at least one hydrogen atom of the unsubstituted cycloalkyl groupmay be substituted with the same substituents described above related tothe alkyl group.

In the present disclosure, the unsubstituted alkenyl group can be linearor branched, and have at least one carbon-carbon double bond. Examplesof the alkenyl group include C₁-C₂₀ alkenyl, C₁₋₁₀ alkenyl, or C₁₋₆alkenyl. Specific examples of the unsubstituted alkenyl group include,but are not limited to ethenyl, propenyl, propenylene, allyl, or1,4-butadienyl. Herein, at least one hydrogen atom of the unsubstitutedalkenyl group may be substituted with the same substituents describedabove related to the alkyl group.

Examples of the compound of Formula (I) may include any one of thefollowing compounds (1) to (224).

Herein, at least one hydrogen atom of the compounds (1) to (224) canfurther be optionally substituted with the aforementioned substituents.

Organic Electronic Device

An organic electronic device comprising the aforementioned compounds isalso provided in the present disclosure.

In one embodiment, the organic electronic device comprises: a firstelectrode; a second electrode; and an organic layer disposed between thefirst electrode and the second electrode, wherein the organic layercomprises any one of the aforementioned compounds.

Herein, the term “organic layer” refers to single layer or multilayersdisposed between the first electrode and the second electrode of theorganic electronic device.

The application of the organic electronic device of the presentdisclosure comprises, but is not limited to, an organic light emittingdevice, an organic solar cell device, an organic thin film transistor,an organic photodetector, a flat panel display, a computer monitor, atelevision, a billboard, a light for interior or exterior illumination,a light for interior or exterior signaling, a heads up display, a fullytransparent display, a flexible display, a laser printer, a telephone, acell phone, a tablet computer, a laptop computer, a digital camera, acamcorder, a viewfinder, a micro-display, a vehicle, a large area wall,a theater or stadium screen, or a sign. Preferably, the organicelectronic device of the present disclosure is applied to an organiclight emitting device, or an organic solar cell device.

In one embodiment, the organic electronic device can be an organic lightemitting device. FIG. 2 is a perspective view showing an exemplarystructure of an organic light emitting device capable of using in oneembodiment of the present disclosure. As shown in FIG. 2, the organiclight emitting device comprises: a substrate 11; an anode 12; a cathode18; and an organic layer comprising a hole injection layer 13, a holetransporting layer 14, a light emitting layer 15, an electrontransporting layer 16 and an electron injection layer 17. However, thepresent disclosure is not limited thereto. Other layers capable ofimproving the luminous efficiency of the organic light emitting device,for example an electron blocking layer or a hole blocking layer, canalso be formed in the organic light emitting device of the presentdisclosure. When the organic light emitting device of the presentdisclosure further comprises the electron blocking layer, the electronblocking layer can be disposed between the hole transporting layer 14and the light emitting layer 15. When the organic light emitting deviceof the present disclosure further comprises the hole blocking layer, thehole blocking layer can be disposed between the electron transportinglayer 16 and the light emitting layer 15.

In one embodiment, the organic light emitting device of the presentdisclosure may include a hole transporting layer, which comprises theaforesaid compounds. In another embodiment, the organic light emittingdevice of the present disclosure may include a hole injection layer,which comprises the aforesaid compounds. In further another embodiment,the organic light emitting device of the present disclosure may includean electron blocking layer, which comprises the aforesaid compounds.However, the present disclosure is not limited thereto.

In one embodiment, the light emitting layer may contain a phosphorescentlight emitting material which may comprise iridium or platinum. Inanother embodiment, the light emitting layer may contain a quantum dotsor semiconductor nanocrystal materials. However, the present disclosureis not limited thereto.

In another embodiment, the organic electronic device can be an organicsolar cell. FIG. 3 is a perspective view showing an exemplary structureof an organic solar cell used herein. As shown in FIG. 3, he organicsolar cell may comprise: a first electrode 21; a second electrode 22;and an organic layer 23 disposed between the first electrode 21 and thesecond electrode 22 and comprising any one of the aforesaid compounds.Herein, the organic layer 23 may be served as a carrier transport layer.

Other objects, advantages, and novel features of the invention willbecome more apparent from the following detailed description when takenin conjunction with the accompanying drawings.

EXAMPLES

The following examples are provided in order to explain thecharacteristics of the present disclosure. However, the presentdisclosure is not limited by the following descriptions of the examples.

The following syntheses are carried out, unless indicated otherwise,under a protected-gas atmosphere. The starting materials can bepurchased from Aldrich or Alfa or obtained in accordance with literatureprocedures.

Synthesis Example 1—Intermediates A1 to A8 and Synthesis Thereof

Intermediates A1 to A8 used for preparing the compounds of Formula (I)are listed in the following Table 1, wherein the numbers below eachintermediates refers to the CAS numbers thereof.

TABLE 1 Intermediates A1 to A8

Intermediate A1 102113-98-4

Intermediate A2 897671-81-7

Intermediate A3 1198395-24-2

Intermediate A4 122-39-4

Intermediate A5 29875-73-8

Intermediate A6

Intermediate A7

Intermediate A8

Intermediates A1 to A5

The intermediates A1 to A5 were purchased from Aldrich or Alfa, and CASNo. were listed above.

Synthesis of Intermediates A6 to A8

The intermediates A6 to A8 can be prepared according to the above SchemeI. The starting materials Ar₁—NH₂ (arylamine) and Br—Ar₂ (arylbromide)are listed in the following Table 2.

Briefly, a mixture of arylbromide (1.0 eq), arylamine (1.05 eq),Pd(OAc)₂ (0.01 eq), 1,1′-Bis(diphenylphosphino)ferrocene (DPPF) (0.04eq), sodium tert-butoxide (1.5 eq), and toluene was taken in a pressuretube and heated at 80° C. for 12 h under N₂ atmosphere. After completionof the reaction, the volatiles were removed under vacuum, and theresulting solution extracted with dichloromethane (3×60 mL). Thecombined organic extract was washed with brine solution, dried overNa₂SO₄, and concentrated to leave a yellow solid. Further, the crudeproduct was purified by column chromatography on silica gel by usinghexane/dichloromethane mixture (2:1 v/v) as an eluent. The analysis dataof the obtained products, i.e. Intermediates A11 to A14, are listed inthe following Table 2.

TABLE 2 EA Arylbromide Arylamine Intermediate Yield(%) (FD-MS)

83.4 C₂₇H₂₁NO (375.46) Intermediate A6

80.2 C₂₇H₂₁NO (375.46) Intermediate A7

81.7 C₂₇H₂₁NO (335.4) Intermediate A8

Synthesis Example 2—Intermediates B1 to B4 and Synthesis Thereof

Intermediates B1 to B4 used for preparing the compounds of Formula (I)are listed in the following Table 3.

TABLE 3 Intermediates B1 to B4

Intermediate B1

Intermediate B2

Intermediate B3

Intermediate B4

Synthesis of Intermediate B1

The intermediate B1 can be prepared according to the above Scheme II.

Step 1: Synthesis of Intermediate B1-1

A mixture of 3-bromodibenzo[a,d]cyclohepten-5-one (86 g, 1.0 eq),N-Bromosuccinimide (106 g, 2 eq), and benzyl peroxide (0.7 g, 0.01 eq)in carbon tetrachloride (430 ml) was heated to 85° C. The reaction wasmonitored by HPLC. After completion of a reaction, the precipitate wasseparated by filtration and washed with MeOH, then purified byrecrystalization. The purified product was concentrated to dryness,whereby a white solid product was obtained in an amount of 123 g in92.3% yield. FD-MS analysis C₁₅H₉Br₃O: theoretical value 444.94,observed value 444.94.

Step 2: Synthesis of Intermediate B1-2

The obtained intermediate B1-1 (116.0 g, 1.0 eq) was dissolved in 960 mlof furan/THF (v/v=2/1), the reaction was cooled to 0° C. and thentreated with KO-t-Bu (87.8 g, 3.0 eq). The reaction was allowed to stirfor 1 h at 0° C. prior to rate up to room temperature and stirred foradditional 12 h. After completion of the reaction, it was quenched by DIwater and the organic layer was recovered by solvent extractionoperation and dried over sodium sulfate. The solvent was removed fromthe organic layer by distillation under reduced pressure, and theresulting residue was purified by silica gel column chromatography. Thepurified product was concentrated to dryness, whereby a light yellowsolid product was obtained in an amount of 46.8 g in 51.1 percent yield.FD-MS analysis C₁₉H₁₁BrO₂: theoretical value 351.19, observed value351.19.

Step 3: Synthesis of Intermediate B1-3

A suspension of the obtained intermediate B1-2 (53.5 g, 1.0 eq) and 5%Pd/C (8.1 g, 0.025 eq) in 535 ml ethyl acetate was stirred for 3-6 hunder a hydrogen atmosphere provided by a balloon of hydrogen. Theresulting mixture was filtered through a pad of celite and washed withethyl acetate, and the filtrate was concentrated under reduced pressureto obtain 100 g (100%) of intermediate B1-3 as a yellow solid. Theobtained compound, intermediate B1-3, was directly used in followingreaction without further purified.

Step 4: Synthesis of Intermediate B1

The obtained intermediate B1-3 (53 g, 1.0 eq) and p-toluenesulfonic acid(57 g, 2.0 eq) in 530 ml of toluene was heated to reflux for 12 hours.The reaction mixture was cooled to room temperature and then quenchedwith a saturated aqueous solution of NaHCO₃ and extracted with CH₂Cl₂.The organic layer was washed with water, brine and dried with anhydrousNa₂SO₄ subsequently. Then the resulting solution was concentrated underreduced pressure and purified by column chromatography on silica gelwith CH₂Cl₂/hexane 1/1 (v/v) as eluent. 46.0 g of intermediate B1 wasobtained as light yellow solids in 91.5% yield. FD-MS analysisC₁₉H₁₁BrO: theoretical value 335.19, observed value 335.19.

Synthesis of Intermediates B2 and B4

The synthesis procedure of intermediate B2 and B4 were used the samemanner as those for preparing the intermediate B1, except that3-bromodibenzo[a,d]cyclohepten-5-one used for preparing the intermediateB1 was replaced by 2-bromodibenzo[a,d]cyclohepten-5-one for preparingthe intermediate B2, replaced by3,7-dibromodibenzo[a,d]cyclohepten-5-one for preparing the intermediateB3, or replaced by dibenzo[a,d]cyclohepten-5-one for preparing theintermediate B4. The intermediates in all the steps, yields and MSanalysis data are listed in the following Table 4.

TABLE 4 Step Starting 1^(st) 2^(nd) Structure

Yield(%) NA 92.3 60.3 Formula NA C₁₅H₉Br₃O C₁₉H₁₁BrO₂ (FD-MS) (444.94)(351.19) Structure

Yield(%) NA 91.5 58.2 Formula NA C₁₅H₉Br₃O C₁₉H₁₁BrO₂ (FD-MS) (444.94)(351.19) Structure

Yield(%) NA 93.7 75.8 Formula NA C₁₅H₈Br₄O C₁₉H₁₀Br₂O₂ (FD-MS) (523.84)(430.09) structure

Yield(%) NA 97.5 63.7 FD-MS (208.26) (366.05) (272.3) (theoretical) Step3^(rd)-1 3^(rd)-2 Structure

Intermediate B1 Yield(%) NA 91.5 Formula C₁₉H₁₃BrO₂ C₁₉H₁₁BrO (FD-MS)(353.21) (335.19) Structure

Intermediate B2 Yield(%) NA 93.5 Formula C₁₉H₁₃BrO₂ C₁₉H₁₁BrO (FD-MS)(353.21) (335.19) Structure

Intermediate B3 Yield(%) NA 93.0 Formula C₁₉H₁₂Br₂O₂ C₁₉H₁₀Br₂O (FD-MS)(432.11) (414.09) structure

Intermediate B4 Yield(%) NA 93.2 FD-MS (274.31) (256.3) (theoretical)

Synthesis Example 3—Intermediate C1 to C4 and Synthesis Thereof

Intermediates C1 to C used for preparing the compounds of Formula (I)are listed in the following Table 5, wherein the numbers below eachintermediates refers to the CAS numbers thereof.

TABLE 5 Intermediates C1 to C4

Intermediate C1 179526-95-5

Intermediate C2 154407-17-7

Intermediate C3 13029-09-9

Intermediate C4

Synthesis of Intermediate C4

A solution of 1-bromo-2-chloro-4-iodobenzene (1.0 eq),4-Chlorophenylboronic acid (1.1 eq), Pd(OAc)₂ (0.95 g, 0.01 eq), PPh₃(4.45 g, 0.04 eq), and 3.0 M K₂CO₃ aqueous solution (58.6 g, 2.0 eq in144 mL H₂O) in toluene (730 mL) was heated under nitrogen at 65° C. for12 h. After cooling to room temperature, the solvent was then removedusing a rotary evaporator, and the remaining substance was purified withcolumn chromatography to obtain intermediate C4 (65%) MS: [M]⁺=301.99.

Synthesis Example 4—Intermediates D1 to D13 and Synthesis Thereof

Intermediates D1 to D13 used for preparing the compounds of Formula (I)are listed in the following Table 6.

TABLE 6 Intermediates D1 to D13

Intermediate D1

Intermediate D2

Intermediate D3

Intermediate D4

Intermediate D5

Intermediate D6

Intermediate D7

Intermediate D8

Intermediate D9

Intermediate D10

Intermediate D11

Intermediate D12

Intermediate D13

Intermediate D14

Intermediate D15

Synthesis of Intermediate D1

The intermediate D1 can be prepared according to the above Scheme III.

Step 1: Synthesis of Spiro Alcohol

To the intermediate C1 (1.0 eq) in anhydrous THF (0.4 M), n-BuLi (1 eq)was added dropwise and stirred at −78° C. After stirring for 20 min,intermediate B4 (0.7 eq) was added to the mixture and the reactionmixture was allowed to warm to room temperature. The reaction wasmonitored by HPLC. After completion of a reaction, the reaction solutionwas quenched with water, and a water layer was extracted with ethylacetate. The extracted solution and an organic layer were combined andwashed with saturated saline, and then dried with magnesium sulfate.After drying, this mixture was subjected to suction filtration, and thenthe filtrate was concentrated. 65 g of spiro alcohol was obtained as alight yellow, powdery solid and was directly used in step 2 withoutfurther purified.

Step 2: Synthesis of Intermediate D1

To the obtained spiro alcohol (1 eq), acetic acid (w/v=1/3 to thereactant) and H₂SO₄ (5 drops) were added, and the mixture was stirred at110° C. for 6 hr. The reaction was monitored by HPLC. After completionof a reaction, the precipitate was separated by filtration. Theremaining substance was purified with column chromatography to obtain 58g of intermediate D1 as white solid in a yield of 93.0%. FD-MS analysisC₃₁H₁₉Br: theoretical value 471.39, observed value 471.39.

Synthesis of Intermediates D2 to D13

The procedures for preparing the intermediates D2 to D13 were similar tothat for preparing the intermediate D1, except that the intermediate B4and the intermediate C1 used for preparing the intermediate D1 weresubstituted with the compounds listed in the following Table 7. Theobtained intermediates D1 to D13 are present in white solids. Inaddition, the yields and MS analysis data of the intermediates D1 to D12are also listed in the following Table 7.

TABLE 7 Yield Formula Intermediate C Intermediate B Spiro-alcoholIntermediate D (%) (FD-MS) Intermediate C1 Intermediate B4

intermediate D1 93.0 C₃₁H₁₉Cl (426.94) Intermediate C2 Intermediate B4

intermediate D2 89.1 C₃₁H₁₉Cl (426.94) Intermediate C3 Intermediate B4

intermediate D3 83.2 C₃₁H₁₉Br (471.39) Intermediate C1 Intermediate B1

intermediate D4 88.7 C₃₁H₁₈BrCl (505.83) Intermediate C2 Intermediate B1

intermediate D5 88.7 C₃₁H₁₈BrCl (505.813) Intermediate C3 IntermediateB1

intermediate D6 86.9 C₃₁H₁₈Br₂ (550.28) Intermediate C1 Intermediate B2

intermediate D7 87.5 C₃₁H₁₈BrCl (505.83) Intermediate C2 Intermediate B2

intermediate D8 83.2 C₃₁H₁₈BrCl (505.83) Intermediate C3 Intermediate B2

intermediate D9 85.8 C₃₁H₁₈Br₂ (550.28) Intermediate C1 Intermediate B3

intermediate D10 79.8 C₃₁H₁₇Br₂Cl (584.73) Intermediate C2 IntermediateB3

intermediate D11 80.1 C₃₁H₁₇Br₂Cl (584.73) Intermediate C3 IntermediateB3

intermediate D12 89.5 C₃₁H₁₇Br₃ (629.18) Intermediate C4 Intermediate B4

Intermediate D13 75.4 C₃₁H₁₈Cl₂ (461.38)

Synthesis of Intermediate D14 and D15

The intermediate D14 and D15 can be prepared according to the aboveScheme IV.

Intermediates D1 or D5 (1.0 eq), Boronic acid (1.1 eq), Pd(OAc)₂ (0.01eq), PPh₃ (0.04 eq), K₂CO₃ (1.5 eq, 3M) in toluene was heated at 100° C.for 12 h. After completion of the reaction, the volatiles were removedunder vacuum, and the resulting solution extracted with dichloromethane(3×60 mL). The combined organic extract was washed with brine solution,dried over Na₂SO₄, and concentrated to leave a yellow solid. Further,the crude product was purified by column chromatography on silica gel.In addition, the yields and MS analysis data of the intermediates D14and D15 are listed in the following Table 8.

TABLE 8 Yield Formula Intermediate D Boronic acid Intermediate D (%)(FD-MS) Intermediate D1

1679-18-1

94.3 C₃₇H₂₃Cl (503.03) Intermediate D14 Intermediate D5

1692-25-7

92.5 C₃₆H₂₂ClN (504.02) Intermediate D15

Synthesis Example 5—Compounds (1) to (30) Synthesis of Compounds (1) to(26)

The compounds of the present disclosure can be synthesized according tothe following Scheme V.

Briefly, a mixture of intermediates D1 to D15 (1.0 eq), intermediates A1to A9 (1.05 eq), Pd(OAc)₂ (0.005 eq), P(t-Bu)₃HBF₄ (0.02 eq), andNaO^(t)Bu (1.5 eq) in toluene (0.3 M) was heated at 90° C. for 8-24 h.After completion of the reaction, the volatiles were removed undervacuum, and the resulting solution extracted with dichloromethane (3×60mL). The combined organic extract was washed with brine solution, driedover Na₂SO₄, and concentrated to leave a yellow solid. Further, thecrude product was purified by column chromatography on silica gel togive final compound with white solid.

Synthesis of Compound (27)

Intermediate A9 (1.0 eq), intermediate D3 (2.1 eq), Pd(OAc)₂ (0.01 eq),P(t-Bu)₃HBF₄ (0.04 eq), and NaO^(t)Bu (3.0 eq) in toluene (0.3M) washeated at 90° C. for 24 h. After completion of the reaction, thevolatiles were removed under vacuum, and the resulting solutionextracted with dichloromethane (3×60 mL). The combined organic extractwas washed with brine solution, dried over Na₂SO₄, and concentrated toleave a yellow solid. Further, the crude product was purified by columnchromatography on silica gel to give final compound with white solid.

The products (1) to (30), the used intermediates, the yields, and the MSanalysis data are listed in the following Table 9.

TABLE 9 Yield EA/ SGM Intermediate A IntermediateD Embodiment (%)(FD-MS) 134 (1) Intermediate A3 Intermediate D1

64.9 C₅₈H₄₁N (751.95) 137 (2) Intermediate A2 Intermediate D1

93.4 C₅₅H₃₇N (711.89) 423 (4) Intermediate A5 Intermediate D1

67.4 C₄₉H₃₁N (633.78) 135 (7) Intermediate A3 Intermediate D2

94.6 C₅₈H₄₁N (751.95) 138 (8) Intermediate A2 Intermediate D2

60.5 C₅₅H₃₇N (711.89) 422 (10) Intermediate A5 Intermediate D2

67.7 C₄₉H₃₁N (633.78) 565 (11) Intermediate A6 Intermediate D2

74.7 C₅₈H₃₉NO (765. 94) 578 (12) Intermediate A7 Intermediate D2

83.6 C₅₈H₃₉NO (765. 94) 564 (31) Intermediate A8 Intermediate D2

71.5 C₅₅H₃₅NO (725.87) 136 (13) Intermediate A3 Intermediate D3

77.8 C₅₈H₄₁N (751.95) 139 (14) Intermediate A2 IntermediateD3

72.8 C₅₅H₃₇N (711.89) 171 (15) Intermediate A1 Intermediate D3

66.2 C₅₅H₃₇N (711.89) 567 (20) Intermediate A4 IntermediateD6

86.0 C₅₅H₃₈N₂ (726.9) 568 (21) Intermediate A4 IntermediateD5

88.9 C₅₅H₃₈N₂ (726.9) 584 (32) IntermediateA1 IntermediateD15

68.3 C₆₀H₄₀N₂ (788.97) 594 (33) IntermediateA1 IntermediateD14

81.9 C₆₁H₄₁N (787.98) 557 (30) IntermediateA4 IntermediateD13

61.2 C₅₅H₃₈N₂ (726.9)

Example—OLED Device Fabrication

A glass substrate having ITO (indium tin oxide) coated thereon to athickness 1500 Å was placed in distilled water containing a detergentdissolved therein, and was ultrasonically washed. Herein, the detergentwas a product manufactured by Fischer Co., and the distilled water wasfiltered twice through a filter (Millipore Co.). After the ITO had beenwashed with detergent for 30 minutes, it was ultrasonically washed twicewith distilled water for 10 minutes followed by isopropyl alcohol,acetone, and methanol, which was then dried, after which it wastransported to a plasma cleaner. Then, the substrate was clean withoxygen plasma for 5 minutes, and then transferred to a vacuumevaporator.

Various organic materials and metal materials were sequentiallydeposited on the ITO substrate to obtain the OLED device of the presentexamples. The vacuum degree during the deposition was maintained at1×10⁻⁶ to 3×10⁻⁷ torr. In addition, the formulas and the code names ofthe materials used in the following OLED devices were listed in thefollowing Table 10.

Preparation of Blue OLED Device

To fabricate the blue OLED device of the present examples, HAT wasfirstly deposited on the ITO substrate to form a first hole injectionlayer with a thickness of 100 Å. HI-2 was deposited on the first holeinjection layer with a dopant HAT (5.0 wt %) to form a second holeinjection layer having a thickness of 750 Å.

Next, HT-1 or compounds of the present disclosure was deposited to forma first hole transporting layer (HT1) with a thickness of 100 Å; and/orHT-2 or compounds of the present disclosure was deposited to form asecond hole transporting layer (HT2) with a thickness of 100 Å. Then, BHwith a dopant BD (3.5 wt %) was deposited on the first or second holetransporting layer to form a light emitting layer having a thickness of250 Å. ET with a dopant Liq (35.0 wt %) was deposited on the lightemitting layer to form an electron transporting layer with a thicknessof 250 Å. Liq was deposited on the electron transporting layer to forman electron injection layer with a thickness of 15 Å. Al was depositedon the electron injection layer to form a cathode with a thickness of1500 Å.

After the aforementioned process, the blue OLED device used in thefollowing test was obtained.

Preparation of Green OLED Device

The preparation of the green OLED device was similar to that of the blueOLED device, except that the second hole injection layer, the lightemitting layer and the electron transporting layer.

Herein, the thickness of the second hole injection layer was 1300 Å. GHwith a dopant GD (10 wt %) was deposited on the first or second holetransporting layer to form a light emitting layer having a thickness of400 Å. The thickness of the electron transporting layer was 350 Å.

Preparation of Red OLED Device

The preparation of the red OLED device was similar to that of the blueOLED device, except that the second hole injection layer, the lightemitting layer and the electron transporting layer.

Herein, the thickness of the second hole injection layer was 2100 Å. RHwith a dopant RD (3.5 wt %) was deposited on the first or second holetransporting layer to form a light emitting layer having a thickness of300 Å. The thickness of the electron transporting layer was 350 Å.

TABLE 10

HI-1

HI-2

HT-1

HT-2

BH

BD

GH

GD

RH

RD

ETD (Liq)

ETOLED Device Measurement

Device performances of the obtained blue, green and red OLED deviceswere measured by PR-650. For the blue and red OLED devices, the datawere collected at 1000 nits. For the green OLED devices, the data werecollected at 3000 nits. Data such as CIE, luminous efficiency (Eff.) anddriving voltage (Voltage) are listed in the following Tables 11 to 13.

TABLE 11 Color Voltage Efficiency Example HT1 HT2 CIE(x, y) (V) (cd/A)Example 1 — SGM136 B 4.30 13.5 (0.136, 0.175) Example 2 — SGM137 B 4.3813.1 (0.135, 0.182) Example 3 — SGM138 B 4.34 13.4 (0.135, 0.184)Example 4 — SGM139 B 4.33 13.4 (0.135, 0.173) Example 5 — SGM171 B 4.1914.1 (0.135, 0.186) Comp Exp (1) HT-1 HT-2 B 4.39 12.1 (0.135, 0.185)

TABLE 12 Color Voltage Efficiency Example HT1 HT2 CIE(x, y) (V) (cd/A)Example 6 — SGM135 G 2.77 82.3 (0.337, 0.625) Example 7 — SGM138 G 3.0277.9 (0.339, 0.623) Example 8 — SGM423 G 3.09 74.4 (0.313, 0.638)Example 9 — SGM557 G 3.02 75.1 (0.314, 0.638) Example 10 — SGM564 G 3.2375.5 (0.314, 0.638) Example 11 — SGM568 G 2.89 74.4 (0.314, 0.639)Example 12 — SGM584 G 3.15 73.7 (0.313, 0.637) Example 13 — SGM594 G2.80 73.6 (0.314, 0.638) Comp Exp (2) HT-1 HT-2 G 2.95 73.5 (0.314,0.637)

TABLE 13 Color Voltage Efficiency Example HT1 HT2 CIE(x, y) (V) (cd/A)Example SGM134 — R 3.50 26.9  14 026 (0.665,0.333) Example — SGM422 R3.96 28.4  15 (0.657, 0.342) Example — SGM564 R 3.65 27.7 116 (0.660,0.338) Example — SGM567 R 4.11 26.4  17 (0.661, 0.338) Example — SGM578R 3.52 24.2  18 (0.660, 0.339) Comp HT-1 HT-2 R 3.65 23.9 Exp (3)(0.661, 0.338)

According to the results shown in Tables 11 to 13, the OLED deviceapplied with the compound of Formula (I) shows improved luminousefficiency and low driving voltage. Therefore, the compound of Formula(I) of the present disclosure can effectively be used as a holetransporting material of an OLED device.

Although the present disclosure has been explained in relation to itspreferred embodiment, it is to be understood that many other possiblemodifications and variations can be made without departing from thespirit and scope of the invention as hereinafter claimed.

What is claimed is:
 1. A compound of Formula (I) below:

wherein, -L_(n1)-NAr₁Ar₂ and -Q_(n2)-NAr₃Ar₄ are each independentlyselected from the group consisting of:

wherein * represents a bonding position; G is deuterium, a substitutedor unsubstituted C₁-C₂₀ alkyl group, a substituted or unsubstitutedC₆-C₄₀ aryl group, a substituted or unsubstituted C₁-C₄₀ heterocyclicgroup, or —NR₁R₂; R₁ and R₂ are each independently hydrogen, deuterium,a substituted or unsubstituted C₁-C₂₀ alkyl group, a substituted orunsubstituted C₆-C₄₀ aryl group, or a substituted or unsubstitutedC₁-C₄₀ heterocyclic group; n1 and n2 are each independently 0 or 1; m1and m2 are each independently 0, 1 or 2, and with the proviso that m1and m2 are not 0 at the same time; and q is 0, 1, or
 2. 2. The compoundof claim 1, wherein m1 is 1; and m2 is 0 or
 1. 3. The compound of claim1, wherein q is 0 or
 1. 4. The compound of claim 1, wherein q is 1; andG is a substituted or unsubstituted C₆-C₄₀ aryl group, a substituted orunsubstituted C₁-C₄₀ heterocyclic group, or —NR₁R₂, in which R₁ and R₂are each independently a substituted or unsubstituted C₆-C₄₀ aryl group.5. The compound of claim 4, wherein G is a substituted or unsubstitutedC₁-C₄₀ heteroaryl group containing a nitrogen atom, or —NR₁R₂, in whichR₁ and R₂ are the same and are a substituted or unsubstituted phenyl,biphenyl or naphthylene.
 6. The compound of claim 5, wherein G isunsubstituted pyridyl, or —NR₁R₂, in which R₁ and R₂ are unsubstitutedphenyl.
 7. The compound of claim 1, wherein the compound is representedby any one of Formulas (I-1) to (I-18) below:

wherein Ar₁, Ar₂, Ar₃, Ar₄, L, Q, G, n1, and n2 represent the same asthose in Formula (I).
 8. The compound of claim 1, wherein the compoundis represented by any one of the following compounds:


9. An organic electronic device, comprising: a first electrode; a secondelectrode; and an organic layer disposed between the first electrode andthe second electrode, wherein the organic layer comprises the compoundof claim
 1. 10. The organic electronic device of claim 9, wherein theorganic electronic device is an organic light emitting device.
 11. Theorganic electronic device of claim 10, wherein the organic layerincludes a hole transporting layer; and the hole transporting layercomprises the compound of claim
 1. 12. The organic electronic device ofclaim 10, wherein the organic layer includes a hole injection layer; andthe hole injection layer comprises the compound of claim
 1. 13. Theorganic electronic device of claim 10, wherein the organic layerincludes an electron blocking layer; and the electron blocking layercomprises the compound of claim 1.